Process for the preparation of styrenated oil-modified alkyd resins using pinane hydroperoxide as catalyst



, rene unsaturatedesteriuterpolyrnersIinHWhich 90=100% The major: oil;eonstituent'pfnheralkydtaresiniispan;

fi a es. Patent ice 2,743,249

PatenteghAgn 125E:

representsthezuppemlimit OfFSOlYEH SYthB-t' mayhezused in t 2,743,349; keepingtwith; the:requirementssofitheipresentinvention By practicing-the. process eof theapresentinvention, is possible,=;tofeoreaceirom;5 %$of;a tstyrenevfiom 5 oundwand, preferablytralQ+ 0%'-.iota styrene compound CATAEYSEE'. 1. b se on thcufinal intcrpolymericreaction producterdee v y y I v pending: for; optimunmresultse npon percentage rof 'g yfifig igfijgs gfig ffiifif EfibfiiifiZfif phthalic :content of; thee-alkyd as welhasitheittype oftoilzs of Mainfimw 'employed-1n;-modifying the::a1kyd: :7;-

No ig il::i% gl7? sati factory; xesultstand theeprcferredrtusefiulxproduc st her eoreaction :must bercficct'edfa -a:temperatqrcaabflvezr150? s Chime-AC1. 260-2 7 0. and below the tempcratnreiat-ywhichrdepfilymerization of polystyrene occurs at a significant rate (290 C.300 :C.), the preferred temperature rangetheing between 160- -v-175: C It is further preferred that the reaction temperature: does not exceed-r2155 1C. significantly ti: :2

In the practice of :the process of the presentinvention, i

PROCESS FOR PREPARATION" OF S'FY' I RENATED OIL-MODIFIED *RESINS USING P-INANE' HYDROPEROXIDE This invention-zrrelates; to: modified :zalk-yds resins. and to the;,pr,ocessr;of; preparingsthesame. :xMorepartiC. larly, this invention relatesitothesprocess 'oitreactingccrs tain styrene eompounds with angoil-modified alkyd resin in a mutually-inert solvent 1having;a boiling-point of at :..vpinanehydroperoxideeis usedaszthecatalystein an amountleast 1=1O; C .:and a Kaurirbutanoltvaluewbetween 24-100, 2 varying -between -.-aboutti0;05%t tocabout 15% by weight in the presence of pinane hydroperoxiden 1;, based: on :the: total :weight-ofl the 'coreaction materials 1 One of the-objects ofvthe presentwinventionis-to pro: From-anoptimum:viewpoint itis preferred .to usefrom duce :a;-tmo dified alkyd,-;resin,; which has-particular, 3P:-

aboutwIe2-% by weighttof thecatalystw plication tin thefieldofi surfacecoating A;furt herobject- The unsaturated.oil-modifiedszalkyd riesins twhichtmay l of thepresentwinvention is to produeeastyrenated alkyd .2 :be employed :in' practicingsthis invention are) the conresin inwthe -presenceqt-of a mutually-inert mineral spirits: a; ventionaL-typeofialkyd resin made :by coreacting ar-polyisolvent; having a bpiling,point ofrtat least 110,? Ciand 1 ;basic acid, an unsaturatedvegetable oileintroduced partlya Kauri-ghutanol;value=b,etween-24rl00. A further} object .or whollyinlhe form of fatty acid 01: monoglyeeririe;and-v of theipresen-t invention-is to produce coating:composimrm, a polyhydric alcohol at an elevated temperature until at tionsn which'tare homogeneous in:-;the liquidistateqand 3isestetification is substantiallycomplete- At least 90% whichnare; homogenequsimapured-fi1rn;.and;which furtherv by weight of the polybasicaci'd component should conhave markedly p o e ep pen e with G P OtI eQ sist of a saturated acid, inc-v, a pqlycarhoxylietacid free of dryingthnehardnessgloss,;:fi 1i lfis ceri nd 60-1; non-benzenoid unsaturation, preferably phthalic, alhol resis c W Ran o j '0fi:-the':prcscntzthoughsothersnmay be-.-employed;t-:-and theuemainder ofinvention wil-Lberdiscussed more f -ull y hereinbelom 4:, I 35 the polybasic acid'inay or -may ib t n dg :Th I have found that P Yd P I Xi 1 -,-a i 'fi cn w polyhydricaalcoholvcompouentmay bewany one of the celerating co-reaction andtcffcc ing almost'completcamacavailable :polyhydrie alcoholstornmixtures thereof; such tion ofitstyrene and unsaturatedoil ,-in1a much-reduced time, zexertssan itnport lf fi,fi s ithcrtowunrccognized in 1 olyglyeolettsueh;as;-hexaethy1ene;glycolgiglycerin s tri 6 ,;o tthatpropcrt esc-ofethe@resulting interpolymer methylolrpropane trimethyloliethane;ipentaerythritolp r y e t f-t sca a yst, t s P ssible o p epare.,s ydipntaerythritoluand thezlikei :---:as ethylene glycol; diethylene' glycol; zpropy-lene glycol;

of the. styrenepis eompletelyscembined- ThSc-.inte unsaturated vegetablezoilrselected from theclassof drying: p y nfir liutionsparet comple ly; vclear t and h mogcnc t and semi-dryingixoils; .AmOllg ithe various: oils which; ous, show ;excellent, stability eharacteristien; and have :may beirused singlyriortineomhination ;as -"modifiers for Wider compatibilities i h 31 s mor ngzmat l the alkyd resin may be mentioned the following:.- china than Sim l r 'P YDI KQ- d byapre ioussm thods. n wood oil, dehydrated castor oil vcastor. oil, linseed oil,

An dd io al shovels-feature, of the i I1t 'P 1Y ,1 --fd': ;perilla oil, soya oil, corn oil, cotton seed oil, talloil, disd: hercin,a.is;,,their zn l ytg 9 5 S Y;: '2,-.tilled talloil fatty acids,- etc; sThese-may bemused singly p atic t y a b nsl olvent rs h ra e preferredllfio 01' in .combination with one. a l fi pl, m ntiQIL -xr o v nts nttheeoatingd u m because, eitheir low cost with relativelyisaturatcd, .oils' such as,c conutitoliveha a, and negligibleodormln this regard, it-v is also desirable. mond andth like. v I that such resin solutionsjolerateat least 5Q cc. and, pref- W Th 'prop fli n f h stymngv pp q l hi h erably, 100 cc. "of mineral spirits ipe'r 10. grams of resin 'Hb oreaetedl with the alkyd,, 're's'i1 1 i s 'dependet on the solution, '-to-insure that no precipitation of resin will 1"de ree ptunsaturationinthepll,asjwell asihetyp occur-during subsequent thinning operations; or in cleanun atn ation that is,i whether conjugated or non-c9 ing of=spray equipment or-brushes. All of the products jugated A further ji portantfl factorfi is the-Oil. 59.. produced aceording to the' teachings-of this invention, tent f h 'alkyd r gih it elf;

- 0 :t t; Q 11, 195 1 We have 01 ride that, to -eifect the. reaetionutoiglve most,

tolerate at least 50 cc. and, in most casesjmore than -1O0- i F o practical viewpoint; the least uwn'saturated oils; v

spirits is Sl ght YJie S but inmos ins tan sei -tw b e -':be used to modify alkyd resins which combine readilyt the desired minimumwalueepecified above In additional-4' with styrene t9 yield h m0 ene us,stable liast-drying to thetuseof Varsol #L'having a Kauri-butanolrvalue of :interpolymers. Linseed; and perilla, oils gccupyt n. 36 and Varsol #2, having-a-Kauri-vbutano1 .valueof 43,, intermfidiategpositign between h h j e u ith V one can makemse of such mutually inert solvents as re pe t' to reacfivity with t11'estyrer 1e compounds ,3 Ultracene having a I auri'-butanol value of 27, kerosene, Alth u h hthalic anhydride is the prcfeliredp0ly-. havinga Kauri-butanol value of 32,rSolvasol No.75 havb li id free f m non-benzenoidg nnsaturation ing aKauri-butanol valueof 7,7, 'S'olvesso- No. 100 ha'vt hi h m y b d i th practice of the 'prjoeess pf the ing a Kiauri butanol value of 90, xylol having a .Kauripresent i m qtvhel-ecomparabk id a b ussgd butanol valueof 93 and the" like. -The Kauri-butanolas maloni *sluqcifiicg gluta fi ,.,sebaclc,.--'adip ;r lf l h m value of toluene is and, as a consequence, this solvent suberic, 'm'alicgazfelaic and the like Whenever available;

the anhydrides of these acids may be used or mixtures of these acids and/ or their anhydrides may be used.

In the place of styrene per se, one may make use of ring substituted chloro styrenes and/or ring substituted alkyl styrenes such as the o, m, and p-chloro styrenes, 2,4-dichloro styrene, 2,5-dichloro styrene, 3,4-dichloro styrene, 0, m, and p-methyl styrenes, 2,4-dimethyl styrene, 2,5-dimethyl styrene, 2,4-diethyl styrene, 2,5-diethyl styrene and the like. Obviously, these styrenes may be used either singly or in combination with one another.

In order that the present invention may be more completely understood, the following examples are set forth in which all parts are parts by weight. These examples are set forth primarily for the purpose of illustration and any specific enumeration of detail contained therein should not be interpreted as a limitation on the case except as indicated in the appended claims.

EXAMPLE 1 Into a suitable reaction vessel equipped with stirrer, thermometer and reflux condenser, there is introduced 148 parts of phthalic anhydride, 73 parts of refined soya oil acids, 38 parts of soya oil, 120 parts of refined castor oil, and 96 parts of glycerin, 95%. The materials are heated to 286 C. for approximately 2 hours using nitrogen gas to remove the water formed and then the charge is cooled to about 245 C. and maintained at that temperature for about 4 hours. A sample of the finished resin is dissolved in mineral spirits to give a 50% solution having the following characteristics: Acid No. 8.5, Viscosity-X-Y (Gardner-Holdt), Color3 (Gardner 1933).

EXAMPLE 2 Interpolymer resin solution Into a suitable reaction vessel equipped with thermometer, stirrer and reflux condenser, there is introduced 55 parts of the alkyd resin prepared according to Example 1 and 60.5 parts of xylol. The mixture is heated to reflux temperature (about 143 C.), whereupon there is added 2.08 parts of pinane hydroperoxide dissolved in 45 parts of methyl styrene. This addition is accomplished slowly over a period of about 1 hour while maintaining the sphere. of reaction at reflux temperature. After the addition is completed, the-resin is refluxed for about 6 hours. The final resin solution having a solids content of 59.6% had a viscosity of X-Y (Gardner-Holdt) and a monomer conversion of 93.7%.

EXAMPLE 3 Interpolymer resin solution Example 2 is repeated in every detail except that in the place of monomeric styrene, there is substituted an equivalent amount of monomeric 2,4-dimethyl styrene. The resultant resin had comparable characteristics.

All. of the interpolymer resin solutions were clear solutions, which, when applied to surfaces such as wood, sheet metal and the like. produced clear films. These resins solutions may be applied to surfaces by any conventional method such as by brushing or spraying. When permitted to airdry, these resins form clear films which exhibit excellent clarity, gloss, gloss retention, resistance to acids, alkalis, organic solvents and abrasion.

I claim:

l. A process which comprises coreacting, at a temperature between 130-215" C., a member selected from the group consisting of styrene, ring-substituted alkylstyrenes and ring-substituted chloro-styrenes and an unsaturated oil-modified alkyd resin, in a mutually inert solvent having a boiling point above 110 C. and a Kauributanol value between 24-100 in the presence of from 0.05% to by weight of pinane hydroperoxide, wherein the oil modifier of said. oil modified alkyd resin is selected from the group consisting of drying and semidrying oils; wherein the polycarboxylic acid used to prepare said alkyd resin consists of at least by weight of a polycarboxylic acid free from non-benzenoid unsaturation.

2. A process which comprises coreacting, at a temperature between 130-215 C., styrene and an unsaturated oil-modified alkyd resin, in a mutually inert solvent, having a boiling point above C. and a Kauri-butanol value between 24-100, in the presence of from 0.05% to 5% by weight of pinane hydroperoxide, wherein the oil modifier of said oil-modified alkyd resin is selected from the group consisting of drying and semi-drying oils; wherein the polycarboxylic acid used to prepare said alkyd resin consists of at least 90% by weight of a polycarboxylic acid free from non-benzenoid unsaturation.

3. A process which comprises coreacting, at a temperature between -215 C., styrene and a soya oilmodified alkyd resin, in a mutually inert solvent, having a boiling point above 110' C. and a Kauri-butanol value between 24-100, in the presence of from 0.05% to 5% by weight of pinane hydroperoxide, wherein the polycarboxylic acid used to prepare said alkyd resin consists of at least 90% by weight of a polycarboxylic acid free from non-benzenoid unsaturation.

4. A clear solution, capable of producing clear film upon air-drying, comprising an inert hydrocarbon solvent having a boiling point above 110 C. and a Kauri-butanol value of 24-100, and having coreacted therein styrene and an unsaturated oil-modified alkyd resin at a temperature between 130-215 C. in the presence of from 0.05% to 5% by weight of pinane hydroperoxide, said solution having 90%-100% of said styrene reacted and said solution having a mineral spirits tolerance greater than 50 cc. per 10 grams of solution, wherein the oil modifier of said oil-modified alkyd resin is selected from the group consisting of drying and semi-drying oils; wherein the polycarboxylic acid used to prepare said alkyd resin consists of at least 90% by weight of a polycarboxylic acid free from non-benzenoid unsaturation.

5. A clear solution, capable of producing clear film upon air-drying, comprising an inert hydrocarbon solvent having a boiling point above 110 C., and a Kauri-butanol value of 24-100, and having coreacted therein styrene and a soya oil-modified alkyd resin, at a temperature between 130-215 C. in the presence of from 0.05% to 5% by weight of pinane hydroperoxide, wherein the polycarboxylic acid used to prepare said alkyd resin consists of at least 90% by weight of a polycarboxylic acid free from non-benzenoid unsaturation.

6. A process which comprises coreacting, at a temperature between 130-215 C., a ring-substituted dichlorostyrene and an unsaturated oil-modified alkyd resin, in a mutually inert solvent, having a boiling point above 110 C. and a Kauri-butanol value between 24-100, in the presence of from 0.05 to 5% by weight of pinane hydropero xide, wherein the oil modifier of said oil-modified alkyd resin is selected from the group consisting of dryingand semi-drying oils; wherein the polycarboxylic acid used to prepare said alkyd resin consists of at least 90% by weight of a polycarboxylic acid free from nonbenzeno'id unsaturation.

7. A. process which comprises coreacting, at a temperature between 130-215 C., a ring-substituted alkylstyrene and an unsaturated oil-modified alkyd resin, in a mutually inert solvent, having a boiling point above 110 C. and a Kauri-butanol value between 24-100, in

the presence of from 0.05 to 5% by weight of pinane hydroperoxide, wherein the oil modifier of said oil-modified alkyd resin is selected from the group consisting of drying and semi-drying oils; wherein the polycarboxylic acid used to prepare said alkyd resin consists of at least 90% by weight of a polycarboxylic acid free from nonbenzenoid unsaturation.

8. A process which comprises coreacting, at a tem- References Cited inthe file of this patent perature between 130-215 C., a ring-substituted chlOI'O- UNITED STATES P ATENTS styrene and an unsaturated oil-modified alkyd resin, in a mutually inert solvent, having a boiling point above 110 2534617 i' 1950 C. and a Kauri-butanol value between 24-100, in the 6 FOREIGN PATENTS presence of from 0.05% to 5% by weight of pinane l hydroperoxide, wherein the oil modifier of said oil-modi 683126 Great Bntam 1952 fied alkyd resin is selected from the group consisting of OTHER REFERENCES y g and semi-drying Oils; wherein the polycarboxylic Fisher et 211.: Ind. and Eng. Chem., pages 671-74,

acid used to prepare said alkyd resin consists of at least 10 M h 1951 Peroxide Digest 90% by weight of a polycarboxylic acid free from nonbenzenoid unsaturation. 

1. A PROCESS WHICH COMPRISES COREACTING, AT A TEMPERATURE BETWEEN 130-215* C., A MEMBER SELECTED FROM THE GROUP CONSISTING OF STYRENE, RING-SUBSTITUTED ALKYLSTYRENES AND RING-SUBSTITUTED CHLORO-STYRENES AND AN UNSATURATED OIL-MODIFIED ALKYD RESIN, IN A MUTUALLY INERT SOLVENT HAVING A BOILING POINT ABOVE 110* C. AND KAURIBUTANOL VALUE BETWEEN 24-100 IN THE PRESENCE OF FROM 0.05% TO 5% BY WEIGHT OF PINANE HYDROPEROXIDE, WHEREIN THE OIL MODIFIER OF SAID OIL MODIFIED ALKYD RESIN IS SELECTED FROM THE GROUP CONSISTING OF DRYING AND SEMIDRYING OILS; WHEREIN THE POLYCARBOXYLIC ACID USED TO PREPARE SAID ALKYD RESIN CONSISTS OF AT LEAST 90% BY WEIGHT OF A POLYCARBOXYLIC ACID FREE FROM NON-BENZENOID UNSATURATION. 